Evidence of a Donor–Acceptor (Ir–H)→SiR 3 Interaction in a Trapped Ir(III) Silane Catalytic Intermediate
| Autor: | Andreas Hansen, Marjolaine Ney, Jean-Pierre Djukic, Mustapha Hamdaoui, Stefan Grimme, Sebastian Dohm, Vivien Sarda, Lydia Karmazin, Corinne Bailly, Nicolas Sieffert |
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| Přispěvatelé: | Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Chimie Théorique (DCM - CT), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Westfälische Wilhelms-Universität Münster (WWU), laboratoire de synthèses Métallo-Induites (LSMI), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
Ligand Organic Chemistry Enthalpy Cationic polymerization Ionic bonding 010402 general chemistry Photochemistry 01 natural sciences Medicinal chemistry 3. Good health 0104 chemical sciences Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Chlorobenzene [CHIM.ANAL]Chemical Sciences/Analytical chemistry Thermochemistry Titration Physical and Theoretical Chemistry ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Organometallics Organometallics, American Chemical Society, 2016, 35 (13), pp.2207-2223. ⟨10.1021/acs.organomet.6b00248⟩ |
| ISSN: | 0276-7333 1520-6041 |
| DOI: | 10.1021/acs.organomet.6b00248⟩ |
| Popis: | The ionic iridacycle [(2-phenylenepyridine-κN,κC)IrCp*(NCMe)][BArF24] ([2][BArF24]) displays a remarkable capability to catalyze the O-dehydrosilylation of alcohols at room temperature (0.4 × 103 < TON < 103, 8 × 103 < TOFi < 1.9 × 105 h–1 for primary alcohols) that is explained by its exothermic reaction with Et3SiH, which affords the new cationic hydrido-Ir(III)-silylium species [3][BArF24]. Isothermal calorimetric titration (ITC) indicates that the reaction of [2][BArF24] with Et3SiH requires 3 equiv of the latter and releases an enthalpy of −46 kcal/mol in chlorobenzene. Density functional theory (DFT) calculations indicate that the thermochemistry of this reaction is largely dominated by the concomitant bis-hydrosilylation of the released MeCN ligand. Attempts to produce [3][BF4] and [3][OTf] salts resulted in the formation of a known neutral hydrido-iridium(III) complex, i.e. 4, and the release of Et3SiF and Et3SiOTf, respectively. In both cases formation of the cationic μ-hydrido-bridged bis-iridac... |
| Databáze: | OpenAIRE |
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